The hydrophosphanation of alkenes, an atom-economy process typically promoted by radicals or metal species, has been shown to take place in the absence of a catalyst, under solvent-free conditions and in a regioselective manner.

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This work was generously supported by the Spanish Ministerio de Ciencia e Innovación (MICINN; CTQ2007-65218 and Consolider Ingenio 2010-CSD2007-00006), the Generalitat Valenciana (GV; PROMETEO/2009/039), and Fondo Europeo de Desarrollo Regional (FEDER). Y. M. acknowledges the Instituto de Síntesis Orgánica (ISO) of the Universidad de Alicante for a grant.